Certain pyridinium compounds and method of making the same



- C-methyl homologues thereof.

Patented Oct. 16,1945 l UNITEDI-STATES PATENT OFFICE.

CERTAIN COMPOUNDSAND METHOD OF MAKING THESAME Melvin De emote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a

corporation of Delaware No Drawing. Original application October 20, 1941, Serial No. 415,765, now Patent No. 2,329,702, dated September 21, 1943. Divided and this application June 3, 1943, Serial No.

8 Claims. (Cl.

This invention relates to a new chemical com-. pound.

One object of our invention is to provide a new material or composition of matter, that is particularly adapted for use as a demulsifier in the resolution "of crudeoil emulsions, and also capabio of use for various other purposes.

Another object is to provide a novel method for producing said new material or composition of matter.

The new composition of matter herein described, consists of a quaternary compound of the pyridine series of the kind hereinafter described in detail.- Members of the pyridine series suitable as reactants include pyridine, alkylated derivatives of pyridine, particularly alkylated derivatives in which the alkyl radical contains three carbon atoms or less, and especially methylated pyridines, i. e., pyridines in which one, two, or three metal groups have been substituted in the nucleus, such as picolines, lutidines and collidines. Also suitable as reactants are the com,'

parable quinolines and isoquinolines, along with represent mixtures of suitable heterocyclic materials which may be used as such, or after suitable purification, without separation into the in-; dividual components.

Specially, then, the compounds herein contemplated as demulsifiers, consist of quaternary nitrogen products obtained by reacting one mole of hydroxy compounds of the following formula R("3-N-4BOH Y in which I is a member of the class consisting of hydroxyethyl radicals, alkyl radicals, aryl radicals, aralkyl radicals, andalicyclic radicals havins-not more than 22 carbon atoms; RCO denotes a radical derived from a detergent-forming monocarboxy acid; and B is a divalent radiganic acids containing eight carbon atoms or more; and not more than 32 carbon atoms, are

characterized by the fact that they combine with alkalis to produce soap or soap-like materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc; For the sake of convenience, theseacids will be indicated by the formula R.COOH. Certain derivatives of detergent-forming acids react with alkali to pro-- duce soap or soap-like materials, and are the obvious equivalent of the unchanged or unmodified detergent-forming acids; for instance, in-

stead of fatty acids, one might employv the chlorinated fatty acids. Instead of the resin acids,

one might employ the hydrogenated resin acids. Instead of naphthenic acids, 'one might employ brominated naphthenic acids, etc.

Coal tar bases a U. S. Patent No. 2,242,837, dated May 20, 1941:, to l cal in which at least one occurrence of the ether It is well known that certain monocarboxy or- The fatty acids are of the type commonly referred to as higher fatty acids; and of course, this is also true in regard to derivatives of the kind indicated, insofar that such derivatives are obtained from higher fatty acids. The petroleum acids include not only naturally-occurring naphthenic acids, but also acids obtained by the oiiidation of wax, parafiln, etc.- Such acids may have as many as 32 carbon atoms. For instance, see

Shields.

As to a'description of a somewhat analogous type compound, see U. S. Patent NO. 2,22,211,

dated May 20, 1941 to Beach. See. also U. S. Patent No. 2,273,181, dated February 17, 1942, to De Groote and Keiser.

The manufacture of substituted amides, or

rather, substituted hydroxylated amides suitable for-reaction with pyridine hydrochloride or the like, is well known. For instance, a selected high molal monocarboxy acid can be reacted with diethanolamine, dipropanolamine, tris(hydroxymethyl) aminomethane, octyl ethanolamine, benzyl ethanolamine, cyclohexyl ethanolamine,

phenyl ethanolamine, dipropanolamine, or the like, to give a substituted amide containing at least one alcoholic hydroxyi in the substituted amino radical, and in some instances, more than one,

. as when derived from diethanolamine or a glyceryl or diglycerylamine derivative. Such amide can then be treated in the conventional manner with a suitable oxyethylating agent, such as ethylene oxide, propylene oxide, glycid, or any one of a numberof other suitable reactants. As to'variety of oxyalkyiating reactants-or reactants in-' tended to introduce hydroxy hydrocarbon groups,

see U. S. Patent No. 2,208,501, dated July 23, 1940, to Hoefielman. As a matter of fact. such reactants, particularly ethylene oxide, can be employed to treat the unsubstituted amide, for instance, oleoamide, ricinoleoamide, stearamide, and the like,-so as to give the same carbon compound as if the derivative had been obtained from monoethanolamine. As previously stated, the oxyethylation of such compounds or similar reaction .procedure involves treatment at comparatively low temperatures, for instance, 120-200" 0., under pressure varying, for example, from 75 lbs. pressure to.300 lbs. pressure, and usually, in the presence of a catalyst consisting of about one-half percent of an alkaline material, such as caustic soda, caustic potash, sodium niethylate, or the like.

Although any of the high molal monocarboxy acids can be converted into the substituted hymixed cocoanut oil is reacted with 4 pound moles of ethylene oxide to give an amide corresponding to the following formula, wherein R.CO repredroxyethyl amides readily by reaction with monoethanolamine, or by other conventional procedure, for instance, reaction of the amide with one mole of ethylene oxide, it is our preference to employhydroxylated amides derived from the higher fatty acids, rather than from petroleum acids, rosin acids, and the like. We have found that by far the most effective demulsifying agents are obtained from. unsaturated fatty acids having 18 carbon atoms. Such unsaturated fatty acids include the fatty acids, such as oleic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. One

may employ mixed fatty acids, as, for example, the fatty acids obtained from hydrolysis of cottonseed oil, soyabean oil, corn oil, etc. Our preferred demulsifler is obtained from unsaturated fatty acids, and more especially, unsaturated fatty acids containing a hydroxyl radical, or unsaturated fatty acids which have been subjected to an oxidation or oxyalkylation step, such as oxyethylation.

Oxyalkylation or the equivalent reactions in essence do nothing more or less than introduce a divalent radical, generally an aliphatic radical,

in which the carbon chain is interrupted at least.

once by oxygen. This is true, for instance, where a one pound mole of a selected amide is treated I with 10 or 15 pound moles of ethylene oxide, or

the like. One may introduce ether linkages. A

In view of what has been said, and in particular, by reference to the aforementioned Haack patent, it will be noted that a compound of the type herein contemplated as a new composition, and particularly as a demulsifier, may be indi-' cated by the following formula:

I Halogen as many as 10 or 15 00.3 e v in which B is a divalent aliphatic radical, containing at least one and less than 15 other linkages; and T is a member of the class consisting of alkyl radicals; aryl radicals; aralkyl radicals;

'alic'yclic radicals; said hydrocarbon radicals having not more than 22 carbon atoms, or is the radical B.OH, where B has its previous significanoe and hydroxyethyl radicals; and B..CO denotes a radical derived from a detergent-forming monocarboxy acid.

,I'he new'compositions' of matter herein contemplated, and specifically for use as demulsifyin'g' agents, may be exemplified by the following examples:

Example 1 One pound mole of the amide derived from sents the acyl radical of the mixed cocoanut oil fatty acids, RCON(C2H4OC2H4OH) 2. One pound mole of such raw material is reacted with one pound mole of pyridine hydrochloride at approximately l50-160 C. in presence of a slight amount of free pyridine. Reaction is continued until complete, as indicated by solubility and absence of the initial reactants. Instead of pure pyridine, a mixture of pyridine bases, for instance,j50%

distilling lip to C.', and 90% distilling at Example 3 The substituted amide derived by reaction between cocoanut oil fatty acids of the kind described and tris(hydroxymethyl) aminomethane,

is substituted in the preceding example, i. e., the example where 6 mols of ethylene oxide are reacted with one mole of an amide togivea suitable raw. material. Such raw material-then is employed in the same way for reaction with pyridinehydrochloride or the like.

Example 4 Thesame procedure is employed as in the pre-. ceding example, except that the, amide is reacted with 9 moles of ethylene oxide instead of 6 moles, all the other procedure being identical.

Example 5 One mole of a substituted amide obtained by reaction between cocoanut oil fatty acids and octylamine is treated with 2 moles of ethylene oxide to give a substituted amide of the following composition:

2T BOON CaHtOCzHtOH wherein RCO has its previous significance and T represents an octyl radical. Such an amide is treated in the same manner as in the preceding example, so as to obtain reaction with pyridine hydrochloride or the like.

Example 6.

Cyclohexylamine in the preparation of an amide, which is subsequently treated with 2 moles of ethylene oxide for each mole of amide, and then with pyridine hydrochloride or the like. I

Example 7 Benzylamine is substituted for octylamine or cyclohexylamine in the two preceding examples, the rest of the procedure remaining the same.

I Example 8 Phenylamine (aniline) is substituted for octylamine, cyclohexylamine, or benzylamine in the three preceding examples, with the rest of the procedure remaining the same.

(Compare this procedure is substituted for octylamine' assaaae Example 9 The same procedureis employed as in the iour previous examples, except that instead of the substituted amide,

'r RCON olnlocimon one employs an amide of thefollowing composition:

. T 7 RC ON V CZHIOCIHlOClHAOH obtained by using an increased proportion 01. ethylene oxide.

Erampie 10 The amide derived from diethanolamine and having the following composition: cirhon RCO C:H4OH

(RCO havingits previous significance) is reacted with one mole of ethylene oxide for each mole of amide to give an amide of the following composition:

which, in turn, is reacted with pyridine hydrochloride in the manner previously'described.

Example 11 As is obvious, other monovalent anions may replace the halogen andserve as a functional I equivalent.

Ricinoleic acid is substituted for cocoanut oil fatty acids in Examples 1-10, preceding.-

Example 12 A drastically-oxidized castor oil having approximately the following characteristics:

. Acid number 13.2 to 25.0 Saponiflcation number 230.5 to 274.0 Iodine number 43.5 to 55:0

Acetyl number 1 164.0 to 192.0

Hydroxyl number 188.0 to 220.0 Percent unsaponifiable matter 1.1 Percent S03- 0.0 Percent ash--. Trace is converted into the substituted amide by reaction' with tris(hydro xymethyl) aminomethane.

' Such amide is substituted for. the amide employed in Examples 1-10, preceding.

' Example 13' Phenylstearic acid is prepared in any suitable manner, as, for example, in the manner described in U. S. Patent No. 2,081,075, dated May Vobach. is converted into an amideby reaction with tris(h'ydroxymethyl) aminomethane, and such amide employed in the manner described in Examples 1-10, preceding;

The manufacture of usually conducted with dinium base halide, hydrobromide, and

an excess of the pyrisuch as the hydrochloride, or usually in the presence 'of a significant amount of the free byridinium base it? self. In many instances, .however, there is no need to use an excess of the pyridinium base and, in fact, no'need to have present any of the free pyridinium base itself, ,or,.at the most, only a trace of the free base.

the above compounds is suitably chlorine.

. .A somewhat analogoususe of our demulsiiying agent is in the removal of a. residual mudsheath which remains after drilling a well by the rotary method. Sometimes the drilling mud contains added calcium carbonate or the like to render the mud susceptible to reaction with hydrochloric acid or the like, and thus expedite its removal.

It has been pointed out that the present invention is concerned not only with a new chemicalcompound for breaking petroleum emulsions of the water-in-oil type in various forms, as already described; but the present invention is also concerned with a method of preparing the same.

Such new compounds are of utility, not only for the purposes specifically enumerated in detail,-

but also find application in, various industries, processes, and for various uses where wetting agents of the conventional type are used. As to some of such uses which are well known, see The expanding application of wetting agents, Chemical Industries, volume 48', page 324 (1941).

Attention is directed to U. S. Patent No. 2,273,181, dated February 17, 1942, to De Groote and Keiser. Said patent contemplates resolution of petroleum emulsions of the water-in-oil type by means of demulsiflers of the following for}- mula type:

. Halogen D- 5 CHa-CHr-NEOCL-R Nos..2,329,700, 2,329,701 and 2,329,703, 811 dated September 21, 1943. I

The present application is a di ision of our pending application Serial No. 415,7 5, filed Oct.

20, 1941, which subsequently matured as U. S. Patent No. 2,329,702, dated September 21, 1943.

Having thus described our invention. what we claim as new and desire to secure by Letters Patentisz, I I

1. A new chemical compound of the following type:

Halogen D5N Y T in which B is a divalent aliphatic radical, con- I, taining at least three andless than 15 ether linkages; and T is a radical having at least carbon atoms; and R00 denotes a radical derived from a detergent-forming monocarboxy acid 8 and not more than 32 carbon having at least 7 atoms; and DEN represents a heterocyclic conipound of the monovalent hydrocarbon. 6 and notmore than 22 pyridine series consisting of pyrl. dine. quinoline, isoquinoline, and C-linked methyl homologues thereof. v

2. A new chemical compound oi the following yp Halogen l C.R in which B is a' divalent aliphatic radical, containing at least .three and less than ether linkages; and T is a monovalent hydrocarbon than 22 radical having at least 6 and not more carbon atoms; and RCO denotes a radical derived from a higheriatty acid; andDEN represents a heterocyclic compound of the pyridine series consisting of pyridine, quinoiine, isoquinoline, and C-linked methyl homologues thereof.

3. A new chemical compound of the following och . in which 8 is a divalent aliphatic radical, containing at'least three and less than-15 ether linkages; and T- is a monovaient vhydrocarbon. radicalhaving at least 6 and not more than 22 carbon atoms; and R.CO denotes a radical derived from a higher unsaturated fatty acid; and DEN represents a heterocyclic compound otthe pyridine series consisting of pyridine, quinoline,

isoquinoline, and C-linked methyl homologues thereof. I 4. A method-for manufacturing chemicalcom- I pounds or the-following type: I

- Halogen 1151/ 'r in which 3 is a divalent aliphatic radical, containing at least three and less than 15 ether' linkages; and-T isa hydrocarbon radical having l aasegasc not more than 22 carbonatoms; and R.CO denotes a radical derived from a detergent-formin monocarboxy acid having at least 8 and not more than 32 carbon atoms; and DEN represents a heterocyclic compound-of the pyridine series consisting cr pyridine, quinoline, isoquinoline, and C-linked methyl homologues thereof; said method involving thesteps of reacting a hydroxy compound of the following type:

in which RCO, B, and T have their prior significance, with a hydrohalide of a hetemcyclic compound of the pyridine series to supply the radical Halogen 5. A new chemical compound ot the following type: r

Halogen in which B is a divalent aliphatic radical, contaihing at least three and less than 15 ether linkages; and T isa monovalent hydrocarbon radical'having at least 6 and not more than 22 carbonato RC0 is the ricinoleyl radical; and DEN represents a'heterocyclic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline, and C-linked methyl homologues thereof.

6. A chemical compound, described as in claim- 5, whereinT is the benzyl radical.

described in claim 

